Copolymers of enol esters of diketones



rneniedoa. 1.1, 1949 2,484,501 COPOLYMERS F ENOL ESTERS OF signor N. Y.,

DIKETONES Hugh J. Hagemeyer, Jr., Kingsport,

to Eastman Kodak Company, a corporation of New Jersey Tenn, u- Rochester,

No Drawing. Application November 26, 1947, Serial No. 788,321

* 16 Claims. (CI. 26046) This invention relates to the preparation of copolymers of acylated enolates of diketones. More specifically this invention relates to a process for preparing new copolymers which comprises copolymerizing an organic polymerizable, unsaturated compound and an acylated enolate of a diketone, such as beta-acetoxypropenyl methyl ketone, which may be represented by the formula:

Previous attempts to prepare the homopolymer of the ester represented by the above formula have heretofore been universally unsuccessful (e. g. see C. D. Hurd, Journal of the American Chemical Society, vol. 66 (1944), page 2013).

It was therefore most unexpected to find that acylated enolates of diketones, which have been demonstrated to be incapable of polymerization, may be advantageously used to prepare valuable copolymers.

It has now been found that copolymers suitable as surface coating compositions, film-forming agents, and the like may be formed by copolymerizing an acylated enolate of a diketone and one or more polymerizable, unsaturated, organic compounds having one or a multiple of CH==C groups.

It is therefore an object of this invention to provide new copolymers of an acylated enolate of a diketone and unsaturated, polymerizable, organic compounds. 1

A further object is to provide a process for preparing new copolymers which are suitable as surface coating compositions, film-coating, and

the like. Other objects will become apparent from a consideration of the following description.

The acylated enolates which I may use in my process may advantageously be prepared by reacting a. ketene with a diketone in the presence of an acid esterification catalyst. Such a process is described in Spence et al. U. S. Patent 2,407,- 301, dated September 10, 1946. It is also possible to prepare these acylated enolates by reacting the desired diketone with an acid halide in the presence of a weak alkaline catalyst such as sodium acetate. (See Nef, Annalen, volume 277 (1893), page 71.) Cther methods will be obvious to those skilled in the art.

2 Acylated enolates which I may use to advantage in my process may be represented by the formula:

wherein R, R1, and R: each represents a member selected from the group consisting of an alkyl group, such as methyl, ethyl, propyl, isopropyl (i. e. an alkyl grouphaving the formula CnH2n+1 where n is a positive integer from 1 to 3) and an aryl group, such as phenyl, 0-, mand p-tolyl, p-propyl phenyl, p-butyl phenyl, etc., i. e. a mononuclear aryl group of the benzene series having 6 to 10 carbon atoms. Typical are methyl-beta-acetoxypropenyl-1 ketone, methylbeta propionyloxypropenyl 1 ketone, methylbeta-butyryloxypropenyl-l ketone, methyl-betaisobutyryloxypropenyl 1 ketone, methyl-betabenzoxypropenyl-l-ketone, ethyl beta-acetoxypropenyl-l-ketone, ethyl beta-propionyloxypropenyl-l-ketone, ethy -beta butyryloxypropenyll-ketone, ethyl beta isobutyryloxypropenyl-lketone, ethyl beta benzoxypropenyl 1 ketone, propyl-beta-acetoxypropenyl 1 ketone, propylbeta isobutyryloxypropenyl 1 ketone, propylbeta-benzoxypropenyl 1 ketone, methyl betaacetcxybutenyl 1 ketone, methyl-beta-isobutyryloxybutenyl-l-ketone, ethyl beta-acetoxypentenyl 1 ketone, ethyl beta isobutyryloxypentenyl-1-ketone,- methyl beta-acetoxyhexenyl-lketone, propyl beta-isobutyryloxyhexenyl-l-ketone, methyl-beta-isobutyryloxy-3-methylbuten- 1-yl ketone, etc. Advantageously enol esters where R, R1, or R1 are methyl or ethyl groups may be used.

The unsaturated, polymerizable organic compounds which I may conveniently employ in my invention contain the group C=t c.

in which the carbon atom C1 is doubly bound to another atom such as carbon, oxygen, or nitrogen, or triply bound to an atom such as carbon or nitrogen. Typical of the polymerizable unsaturated organic compounds which I may use are the acrylates, the methacrylates, fumarates, maleates, vinyl esters, alkyl alkenyl ketones, alphaacyloxyalkenyl nitriles, alkenyl fumarate, isopropyl nitriles. and hydrocarbons containing conjuwherein R3 represents a hydrogen atom or a methyl group, and R4 represents an alkyl group such as methyl, ethyl, propyl, butyl, isobutyl, secondary and tertiary butyl (i. e., an alkyl group having the formula CnH2n+l where n is a positive integer from 1 to 4), an alkenyl group such as vinyl, allyl, methallyl, crotyl, (i. e., an alkenyl group having the formula CgiH2n-l where n is a positive integer from 2 to 4) or'an aralkyl group such as benzyl, beta-phenylethyl, beta-phenylbutyl (i. e., an aralkyl group ofthe benzene series having 7 to 10 carbon atoms). Typical of the acrylates and methacrylates are methyl acrylate, methyl methacrylate, ethyl acrylate. n-propyl methacrylate, n-butyl methacryiate, benzyl acrylate, allyl methacrylate, methallyl acrylate. etc

The maleates or fumarates which I mayadvantageously use in my process may be represented by the formula:

wherein R5 and Rs each represents a member selected from the group consisting of an alkyl group, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, secondary and tertiary butyl (i. e. an alkyl group having the formula CnH2n+1 where n is a positive integer from 1 to 4), an alkenyl group such as vinyl, allyl, methallyl, crotyl, (i. e. an alkenyl group having the formula CnHiin-l where n is a positive integer from 2 to 4), and an aralkyl group such as benzyl, betaphenylethyl, beta-phenylpropyl, i. e. an aralkyl group of the benzene series having 7 to 10 carbon atoms. Typical are dimethyl maleate, dimethyl fumarate, diethyl maleate, diethyl fumarate, dipropyl maleate, dipropyl fumarate, diisopr'opyl maleate, diisopropyl fumarate, dibutyl maleate, dibutyl fumarate, divinyl maleate, divinyl fumarate, diallyl maleate, diallyl fumarate, dimethallyl maleate, dimethallyl fumarate, methyl allyl maleate, butyl methallyl maleate, butyl methallyl allyl fumarate, dibenzyl maleate, dibenzyl fumarate, butyl benzyl maleate, butyl benzyl fumarate. etc.

The unsaturated esters which I may advantageously use may be represented by the formula:

wherein R1 represents a member selected from the group consisting of hydrogen, an alkyl group, such as methyl, ethyl, propyl, isopropyl, (i.. e. an alkyl group having the formula CnH2n+1 where n is a positive integer from 1 to 3), a

and R0 represents hydrogen or methyl, an aryl group such as phenyl, 0-, m-, andp tolyl (i. e. a

mononuclear aryl group having 6 to 10 carbon atoms), and a group where R9 has the above designated definition, and Rs represents a member selected from the group consisting of a hydrogen atom and a methyl (CH3) group. Typical are vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, divinyl succinate, divinyl adipate, divinyl phthalate, vinyl benzoate, isopropenyl acetate, isopropenyl butyrate, etc. Advantageously I may use esters where R: is an alkyl radical such as methyl, ethyl, etc. and R: is a hydrogen atom, i. e; vinyl acetate, vinyl propionate, etc.

The alkenyl ketones which I may use may be represented by the formula:

1 Rio( J u wherein R10 represents a member selected from the group consisting of an alkyl group, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, secondary and tertiary butyl (i. e. an alkyl group having the formula CnH21i+l wherein n is a positive integer from 1 to 4), and an alkenyl group such as vinyl, allyl, methallyl, isopropenyl, crotyl,

etc. (i. e. an alkenyl group having the formula CnH2n-1 where n is a positive integer from 2 to 4), and R11 is an alkenyl group, such as vinyl, allyl, methallyl, isopropenyl. crotyl, etc. (i. e. an alkenyl group having the formula CnH2n-l where n is a positive integer from 2 to 4). Typical are methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, butyl vinyl ketone, methyl lsopropenyl ketone, ethyl isopropenyl ketone, propyl isopropenyl ketone, methyl ally] methallyl ketone, butyl crotyl ketone, diallyl ketone, divinyl ketone, dimethallyl ketone, vinyl isopropenyl ketone, etc. Advantageously I may use the alkyl alkenyl ketones where R10 is an alkyl group, such as methyl or ethyl, and R11 is an alkenyl group such as vinyl or isopropenyl.

The acyloxy alkenyl nitriles which I may advantageously use may be represented by the formula:

wherein R12 represents an alkyl group, such as methyl, ethyl, propyl, isopropyl, butyl or isobutyl (i. e. an alkyl group having the formula cnHZn-l-l where n is a positive integer from 1 to 4). Typical are a-acetoxyacrylonitrile, a-propionyloxyac rylonitrile, a-isobutyryloxyacrylonitrile, etc.

The alken'yl nitriles which I may use may be represented by the formula:

wherein R1: represents a hydrogen atom or an,

. excess acylated enolate cal are the aliphatic dioletins such as butadienel,8, isoprene, piperylene, 2,3-dimethyl-L8-butadiene, 1,3-hexadiene, etc., the cycloaliphatic diolenns, such as cyciopentadiene, 1,3-cyclohexadiene, 2,2,l-bicycioheptadiene-L8, etc., and arounsaturated, polymerizable, organic compound as defined by the above formulas. Ordinarily I only employ one of the above unsaturated, organic compounds, however I may use two or more such compounds in a single run to advantage. Generally 1 use lined by the above formulae in the polymerization of an acylated enolate of a diketone.

The velocity of the copolymerization may be accelerated to a considerable extent by heating, or by the use of polymerization catalysts which are known to accelerate the polymerization of vinyl-type compoun Exemplary of such catalysts are the organic peroxides (e. g. benzoyl peroxide, acetyl peroxide, acetyl benzoyl peroxide, lauroyl peroxide, oleoyl peroxide, etc.) hydrogen peroxide, perborates (e. g. alkali metal perborates), and persulfates (e. g. alkali metal persulfates).

The temperature at which the copolymerization is effected may vary from ordinary room temperature (approximately C.) to approximately (SO-65 C. The copolymerization can also be carried out by the bead or emulsion method in which water or some other medium in which the monomers are insoluble is employed as a dispersing medium, with or without emulsifying agents. The emulsion method of copolymerization is particularly suitable where a large ratio of the acylated enolate of the diketone to the polymerizable, unsaturated, organic compounds is desired.

The copolymerization can also be eflected in the presence of an inert diluent, such as benzene, toluene, etc., which is advantageously a solvent for the copolymer.

The ratio of acylated enolate of a diketone to polymerizable, unsaturated organic compound in the monomeric mixture prior to polymerization may be varied over a relatively wide range, depending on the specific nature of the reactants and the properties desired in the copolymer. If a comparatively large ratio of acylated enolate to unsaturated compound has been used, the resulting product may be only slightly viscous or may consist of the polymer dissolved in the excess of acylated enolate. To obtain the resinous copolymer it is merely necessary to add a solvent to the reaction mixture which dissolves the but not the copolymer, thus precipitating the copolymer. Such solvents as methanol, ethanol, etc, are useful for this purpose, although acetic acid, diethyl ether, etc. may also be used. Advantageouslyl can use from i to 10 .partsby weight of acylated enolate to 10 to 1 parts by weight of another polymerizable, unsaturated, organic compound in preparing my new copolymers, however, a wider range can be used if desired. The copolymers thus prepared in accordance with the process of my invention can contain as high as 50 weight per cent or the acylated enolate oi the diketone. Especially useful resins were prepared which contained from 5 to weight per cent of the acylated enolate of a dikctonc.

1-2 of the unsaturatedv compounds de- The following examples will further serve to characterize my invention.

Example I Seven ('1) grams of methyl-beta-acetoxy propenyl ketone having the formula:

0 CH: 0 CH+1 JCH=( JO-l -C13s and five (5) grams of styrene were intimately Example II Five (5) grams of methyl-beta-acetoxypropenyl ketone having the formula:

and ten (10) grams of methyl methacrylate were intimately mixed, and 1% (0.15 gm.) of acetyl benzoyl peroxide added. The mixture was then heated at C. for 96 hours. The residue was cooled and a clear colorless polymer was obtained. The polymer was then dissolved in acetone and precipitated by the addition of methanol to give a white, fibrous substance. when a molecularb equivalent amount of ethyl acrylate replaces the methyl methacrylate in the above example, a resinous copolymer suitable for molding can be obtained.

Example III Five (5) grams of methyl-beta-acetoxypropenyl ketone having the formula:

turewas then heated at 50 and five (5) grams of methyl isopropenyl ketonc were intimately mixed, and 1% (0.1 gm.) of acetyl peroxide added. The mixture was then heated at 50 C. for 144 hours. The residue was cooled and a soft, clear resin was obtained. The polymer was then dissolved in acetone and precipitated by the addition of methanol to give a white, fibrous solid containing 2.50% by weight acetyl. When 7 grams of diisopropyl fumarate were used in place of the 5 grams of methyl isopropenyl ketone in the above example, a resinous solid suitable for molding was obtained. The properties of the resinous fumarate copohrmer compared favorably with those of the copclymer of Example 2. Dibutyl maleate gave a copolymer likewise having properties similar to the copolymer of Example 2.

Example IV and five (5) grams 0! a-acetoxy acrylonitrile were intimatehr mixed, and 1% (0.1 gm.) of acetyl benzoyl peroxide added. The resulting mix- C. for 96 hours. The

residue was cooled and a pale yellow resin was obtained. The copolymer was then dissolved in acetone and precipitated by the addition of methanol to give a white, powdery substance containing 8.1 nitrogen. when 5 grams of methylbeta-benzoxypropenyl ketone replaced the methyl-beta-acetoxypropenyl ketone in the above example, a fibrous, colorless resin was obtained.

Example V Ten 10) grams of methyl-beta-acetoxy propenyl ketone having the formula:

and five (5) grams of vinyl acetate were intimately mixed, and 0.5% (0.075 g.) of acetyl peroxide added. The mixture was heated at 70 C. for 72 hours. The resulting resin was cooled and a soft, clear polymer containing considerable monomer was obtained. The resin was dissolved in acetone, and precipitated with methanol to give a white, fibrous solid. On analysis, the copolymer was found to contain 59.3% by weight of acetyl. This corresponds to a copolymer containing one part of aoylated enolate to three parts of vinyl acetate.

I claim:

1. A resinous copolymer containing in the polymer molecule from 5 to 50% by weight of an acetylated enolate represented by the formula:

wherein R3 represents a member selected from the group consisting of a hydrogen atom and a methyl group, and R4 represents a member selected from the group consisting of .an alkyl group of the formula CnHZn-H wherein n is a positive integer from 1 to 4, a benzyl group and a ,9- phenylethyl group; esters represented by the formula:

o m-O-tL-oLbCH- -OR.

.wherein R5 and Rs each represents an alkyl group of the formula CnH2n+1 where n is a positive integer from 1 to 4; vinyl esters represented by the formula R7COOCH=CH2 wherein R7 represents an alkyl group of the formula CnH2n+l wherein n is a positive integer from 1 to 3; alkenyl ketones represented by the formula:

wherein R represents an alkyl group of the formula cnHzn-l-l wherein n is a positive integer from 1 to 4 and R11 represents an alkenyl group of the formula CnHZMl wherein n is a positive 8 integer from 2 to 4; and 'a-acylomcrylonitriles represented by the formula:

wherein R1: represents an alkyl group of the formula CnHZn-l-l wherein n is a positive integer from 1 to 3. I

2. A resinous copolymer containing in the polymer molecule from 5 to 25% by weight of an acetylated enolate represented by the formula:

0 on, om-lt-orhtz-o'o CCH: and from '75 to by weight of an ester represented by the formula:

' CH:=CCOOR4 wherein R4 represents an alkyl group of the formula CnH21r+l wherein n is a positive integer from 1 to 4.

3. A resinous copolymer containing in the polymer molecule from 5 to 25% by weight of an acetylated enolate represented by the formula:

and from 75 to 95% by weight of an alkenyl ketone represented by the formula:

0 1o Rn wherein Rm represents an alkyl group of the formula CnH2n+1 wherein n is a positive integer from 1 to 4 and R11 represents an alkenyl group of the formula CnHZn-l wherein n is a positive integer from 2 to 4.

5. A resinous copolymer containing in the polymer molecule from 5 to 25% by weight of an acetylatd enolate represented by the formula:

and from 75 to 95% by weight of an alkenyl ke-' tone represented by the formula:

0 CR PE-Ru wherein R11 represents an alkenyl group of the formula CIIHZn-l wherein n is from 2 to 4.

6. A resinous copolymer containing in the polymer molecule from 5 to 25% by weight of an acetylated enolate represented by the formula:

mer molecule from 5 to 25% by weight of an acetylated enolate represented by the formula:

0 on. om-t-onJz-ooo-cm a positive integer and from '15 to 95% by weight of a vinyl ester represented by the formula:

m-coocn- -cm wherein R1 represents an alkyl group of the formula CnHan+1 wherein n is a positive integer from 1 t 3.

8. A resinous copolymer containing in the polymer molecule from to by weight of an acetylated enolate represented by the, formula:

and from '75 to 95% by weight of vinyl acetate. 9. A process for preparing resinous copolymers which comprises heating in the presence of a peroxide polymerization catalyst a mixture consisting of from 1 to 10 parts by weight of an acetylated enolate represented by the formula:

(I) R1 R- J-oH= :ooo-0H= wherein R and R1 each represents a member selected from the group consisting of a methyl group and an ethyl group, and from 1 to 10 parts by weight of another unsaturated compound selected from the group consisting of styrene; acrylonitrile; a-methacrylonitrile; esters represented by the formula:

wherein R5 and Rs each represents an alkyl group of the formula CnH2n+1 where n is a positive integer from 1 to 4; vinyl esters represented by the formula:

wherein R1 represents an alkyl group of the formula CnHfln-i-l wherein n is a positive integer from 1 to 3: alkenyl ketones represented by the formula:

O iva-R11 wherein R represents an alkyl group of the formula CnHIn-i-i wherein n is a positive integer from 1 to 4 and R11 represents an alkenyl group -of the formula CnHiln-I wherein n is a positive integer from 2 to 4; and e-acyloxyacryionitriles represented by the formula:

wherein R1: represents an alkyl group of the formula C1|H2n+1 wherein n is a positive integer from 1 to 3.

10. A process for preparing resinous copolymers which comprises heating in the presence of a peroxide polymerization catalyst a, mixture con- 10 sisting of from 1 to 10 parts by weight of an acetylated enolate represented by the formula:

' O CH:

cnr-t'i-ciko-poo-om and from 1 to 10 parts by weight of an ester represented by the formula:

CH,==CCOOR| H, wherein R4 represents an alkyl group of the formula C1|H2n+1 wherein n is a positive integer from 1 to 4..

11. A process for preparing resinous copolymers which comprises heating in the presence of a peroxide polymerization catalyst a mixture consisting of from 1 to 10 parts by weight of an acetylated enolate represented by the formula:

on, oH,0-cH=c-0oo-c11 and from 1 to 10 parts by weight of methyl a-methacrylate.

12. A process for preparing resinous copolymers which comprises heating in the presence of a peroxide polymerization catalyst a mixture consisting of from 1 to 10 parts by weight of an acetylated enolate represented by the formula:

and froml to 10 parts by weight of an alkenyl peroxide polymerization catalyst a mixture con-' sisting of from 1 to 10 parts by weight of an acetylated enolate represented by the formula:

and from 1 to 10 parts by weight of an alkenyl ketone represented by the formula:

0 CHr-QF-Ru wherein R11 represents an alkenyl group of the formula omit-1 wherein n is a positive integer from 2 to 4.

14. A process for preparing resinous copolymers which comprises heating in the presence of a peroxide polymerization catalyst a mixture consisting of from 1 to 10 parts by weight of an acetylated enolate represented by the formula:

- om- -cikc-ooo-wm and from 1 to 10 parts by weight of methyl isopropenyl ketone.

15. A process for preparing resinous copolymers which comprises heating in the presence of a peroxide polymerization catalyst a mixture consisting of from 1 to 10 parts by weight of an acetylated enolate represented by the formula:

1 and from 1 to 10 parts by weight of a vinyl ester peroxide polymerization catalyst a mixture conrepresented by the formula: sisting of from 1 to 10 parts by weight of an RFCOOCH=CH, acetylated enolate represented by the formula: wherein R1 represents an alkyl group 0f 5 i 0 CH formula CnHIn-i-l wherein n is a positive integer CHr-Hl-CH=-OOCCH; from 1 to 3. and from 1 to 10 parts by weight of vinyl acetate. 16. A process for preparing resinous copolymers H EM JR comris hatin inth r en' 1 which 9 88 e 8 F p as ce 9 a No references cited. 

